1.Synthesis, spectroscopic properties and photodynamic activity of porphyrin-fullerene C60 dyads with application in the photodynamic inactivation of Staphylococcus aureus.
Ballatore MB1, Spesia MB1, Milanesio ME1, Durantini EN2. Eur J Med Chem. 2014 Aug 18;83:685-94. doi: 10.1016/j.ejmech.2014.06.077. Epub 2014 Jul 1.
A covalently linked porphyrin-fullerene C60 dyad 5 was synthesized by 1,3-dipolar cycloaddition using 5-(4-formylphenyl)-10,15,20-tris[3-(N-ethylcarbazoyl)]porphyrin, N-methylglycine and fullerene C60. Methylation of 5 was used to obtain a cationic dyad 6. Spectroscopic properties were compared in toluene, N,N-dimethylformamide (DMF) and toluene/sodium bis(2-ethylhexyl)sulfosuccinate (AOT)/water reverse micelles. Absorption spectra of the dyads were essentially a superposition of the spectra of the porphyrin and fullerene reference compounds, indicating a very weak interaction between the chromophores in the ground state. The fluorescence emission of the porphyrin moiety in the dyads was strongly quenched by the attached fullerene C60 unit. The singlet molecular oxygen, O2((1)Δg), productions (ΦΔ) were strongly dependent on the solvent polarity. Similar ΦΔ values were obtained for 5,10,15,20-tetrakis[3-(N-ethylcarbazoyl)]porphyrin (TCP) in both solvents.
2.Desymmetrized Vertex Design for the Synthesis of Covalent Organic Frameworks with Periodically Heterogeneous Pore Structures.
Zhu Y1, Wan S2, Jin Y1, Zhang W1. J Am Chem Soc. 2015 Nov 4;137(43):13772-5. doi: 10.1021/jacs.5b09487. Epub 2015 Oct 21.
Two novel porous 2D covalent organic frameworks (COFs) with periodically heterogeneous pore structures were successfully synthesized through desymmetrized vertex design strategy. Condensation of C(2v) symmetric 5-(4-formylphenyl)isophthalaldehyde or 5-((4-formylphenyl)ethylene)isophthalaldehyde with linear hydrazine linker under the solvothermal or microwave heating conditions yields crystalline 2D COFs, HP-COF-1 and HP-COF-2, with high specific surface areas and dual pore structures. PXRD patterns and computer modeling study, together with pore size distribution analysis confirm that each of the resulting COFs exhibits two distinctively different hexagonal pores. The structures were characterized by FT-IR, solid state (13)C NMR, gas adsorption, SEM, TEM, and theoretical simulations. Such rational design and synthetic strategy provide new possibilities for preparing highly ordered porous polymers with heterogeneous pore structures.
3.De novo biosynthesis of Gastrodin in Escherichia coli.
Bai Y1, Yin H2, Bi H2, Zhuang Y2, Liu T3, Ma Y4. Metab Eng. 2016 May;35:138-47. doi: 10.1016/j.ymben.2016.01.002. Epub 2016 Jan 12.
Gastrodin, a phenolic glycoside, is the key ingredient of Gastrodia elata, a notable herbal plant that has been used to treat various conditions in oriental countries for centuries. Gastrodin is extensively used clinically for its sedative, hypnotic, anticonvulsive and neuroprotective properties in China. Gastrodin is usually produced by plant extraction or chemical synthesis, which has many disadvantages. Herein, we report unprecedented microbial synthesis of gastrodin via an artificial pathway. A Nocardia carboxylic acid reductase, endogenous alcohol dehydrogenases and a Rhodiola glycosyltransferase UGT73B6 transformed 4-hydroxybenzoic acid, an intermediate of ubiquinone biosynthesis, into gastrodin in Escherichia coli. Pathway genes were overexpressed to enhance metabolic flux toward precursor 4-hydroxybenzyl alcohol. Furthermore, the catalytic properties of the UGT73B6 toward phenolic alcohols were improved through directed evolution.
4.Effect of acid-catalyzed formation rates of benzimidazole-linked polymers on porosity and selective CO2 capture from gas mixtures.
Altarawneh S1, İslamoğlu T1, Sekizkardes AK1, El-Kaderi HM1. Environ Sci Technol. 2015 Apr 7;49(7):4715-23. doi: 10.1021/es505760w. Epub 2015 Mar 12.
Benzimidazole-linked polymers (BILPs) are emerging candidates for gas storage and separation applications; however, their current synthetic methods offer limited control over textural properties which are vital for their multifaceted use. In this study, we investigate the impact of acid-catalyzed formation rates of the imidazole units on the porosity levels of BILPs and subsequent effects on CO2 and CH4 binding affinities and selective uptake of CO2 over CH4 and N2. Treatment of 3,3'-Diaminobenzidine tetrahydrochloride hydrate with 1,2,4,5-tetrakis(4-formylphenyl)benzene and 1,3,5-(4-formylphenyl)-benzene in anhydrous DMF afforded porous BILP-15 (448 m(2) g(-1)) and BILP-16 (435 m(2) g(-1)), respectively. Alternatively, the same polymers were prepared from the neutral 3,3'-Diaminobenzidine and catalytic amounts of aqueous HCl. The resulting polymers denoted BILP-15(AC) and BILP-16(AC) exhibited optimal surface areas; 862 m(2) g(-1) and 643 m(2) g(-1), respectively, only when 2 equiv of HCl (0.